Crosslinked polyurethanes

ABSTRACT

The invention relates to a crosslinked polyurethane comprising 
 
A) at least one polytetrahydrofuran of the formula  
                 
B) at least one compound which contains more than 2 active hydrogen atoms per molecule C) at least one compound which contains at least 2 active hydrogen atoms per molecule and at least one ionogenic and/or ionic group per molecule, where the groups may be anionogenic, anionic, cationogenic or cationic D) at least one diisocyanate E) optionally a compound different from B) and C) which contains at least 2 active hydrogen atoms and has a molecular weight of from 60 to 5000 or the salts thereof.

The present invention relates to crosslinked polyurethanes based onpolytetrahydrofurans, and to the use thereof in cosmetic and/orpharmaceutical preparations.

In cosmetics, hair-treatment compositions which are present, forexample, as hair setting compositions or hair spray, are used forsetting, improving the structure of and styling the hair. Thehair-treatment compositions consist primarily of a solution offilm-forming resins or synthetic polymers. To date, the following filmformers have mainly been used in hair-treatment compositions: shellac,homopolymers and copolymers of N-vinylpyrrolidone, copolymers of vinylethers/maleic half-esters, of (meth)acrylic acid or esters and amidesthereof and crotonic acid with vinyl esters.

The hair-treatment compositions are applied to the hair in the form ofsolutions, preferably as ethanolic solutions, by spraying. After thesolvent has evaporated, the hair is retained in the desired shape at themutual points of contact by the polymer which remains. The polymersshould, on the one hand, be sufficiently hydrophilic to be able to bewashed out of the hair, and on the other hand they should be hydrophobicso that the hair treated with the polymers retains its shape even inhigh atmospheric humidity and does not stick together.

The polymeric film formers known to date, such as polyvinylpyrrolidones, however, in most cases exhibit the disadvantage of anexcessively high water absorption at increased atmospheric humidity.This property leads, inter alia, to an undesired stickiness of the hairand to a loss of the setting and thus to a collapse of the hairstyle.If, on the other hand, the resistance to high atmospheric humidity isimproved, e.g. in the case of copolymers of N-vinylpyrrolidone and vinylacetate, then the setting action of the film suffers as a result and mayeven lead to an unpleasant dusting and a flaky deposit. In addition, theability to be washed out during washing of the hair, in particular, ishindered. It is an object of the present invention to provideauxiliaries for cosmetic and pharmaceutical preparations.

It is an object of the present invention to provide novel cosmeticcompositions, in particular hair-treatment compositions based onpolyurethane, which, on the one hand, can be used as hair-settingcompositions, but, on the other hand, also have a good ability to bewashed out (redispersibility). They should impart smoothness andsuppleness to the hair.

Of particular interest are polymeric film formers which impart thedesired flexibility to the hair and at the same time have no or lowstickiness.

We have found that this object is achieved by crosslinked polyurethanescomprising

-   -   A) at least one polytetrahydrofuran of the formula    -   B) at least one compound which contains more than 2 active        hydrogen atoms per molecule    -   C) at least one compound which contains at least 2 active        hydrogen atoms per molecule and at least one ionogenic and/or        ionic group per molecule, where the groups may be anionogenic,        anionic, cationogenic or cationic    -   D) at least one diisocyanate.

The crosslinked polyurethanes according to the invention are suitable ascosmetic and/or pharmaceutical auxiliaries, in particular as filmformers.

EP 656 021 B1 describes the use of

-   -   a) at least one compound which contains two or more active        hydrogen atoms per molecule,    -   b) at least one acid- or salt-containing diol and    -   c) at least one diisocyanate    -   with a glass transition temperature of at least 15° C. and acid        numbers of from 12 to 150, or the salts of these polyurethanes        in cosmetic preparations and as binders or coverings in        pharmaceutical preparations.

Examples which are mentioned are polyurethanes from polyesters. EP 656021 B1 does not describe polyurethanes with polytetrahydrofurans.

Compared to the polyurethanes described in EP 656 021 B1, thepolyurethanes according to the invention have good flexibility, coupledwith low stickiness.

EP-A-619 111 describes the use of polyurethanes based on organicdiisocyanates, diols and 2,2-hydroxymethyl-substituted carboxylates ofthe formula

in which A is a hydrogen atom or a C₁-C₂₀-alkyl group, in hair-settingcompositions. At least some of the carboxyl groups here are neutralizedwith an organic or inorganic base. The diols here have a molecularweight in the range from 300 to 20 000, the suitable diol componentbeing, inter alia, also polytetrahydrofurans. However, none of theworking examples describes a polyurethane based on apolytetrahydrofuran. Films based on these polyurethanes are soft andsticky and the hair-setting compositions based thereon are accordinglyin need of improvement.

The polyurethanes described in the last-mentioned publications cansatisfy the requirements for hair-setting polymers only partially. Forexample, the desired suppleness of the hair in the case of all of theabovementioned polyurethane-based products is in need of improvement.

EP 672 076 B1 describes the use of cationic polyurethanes and polyureascomprising

-   -   (a) at least one diisocyanate which may have already been        reacted beforehand with one or more compounds which contain two        or more active hydrogen atoms per molecule, and    -   (b) at least one diol containing one or more tertiary,        quaternary or protonated tertiary amine nitrogen atoms, primary        or secondary amino alcohol, primary or secondary diamine or        primary or secondary triamine    -   with a glass transition temperature of at least 25° C. and an        amine number of from 50 to 200, based on the nonquaternized or        protonated compounds, or other salts of these polyurethanes and        polyureas as auxiliaries in cosmetic and pharmaceutical        preparations.

Polyurethanes containing cationic groups form hygroscopic films whichare sticky. They therefore generally do not satisfy the requirementswith regard to shine and natural appearance which are placed onhair-setting polymers.

WO 01/16200 describes water-soluble or water-dispersible polyurethanescomprising an oligomer a) of

-   -   A) at least one diisocyanate,    -   B) at least one compound with at least two groups which are        reactive toward isocyanate groups and which is chosen from        -   B1) aliphatic and cycloaliphatic polyoles, polyamines and/or            amino alcohols,        -   B2) polyetheroles and/or diaminopolyethers,        -   B3) polysiloxanes with at least two active hydrogen atoms            per molecule,        -   B4) polyester polyoles,        -   and mixtures thereof, and    -   C) optionally at least one dicarboxylic acid and/or        hydroxycarboxylic acid,    -   where the oligomer contains, per molecule, at least two urethane        and/or urea groups and additionally at least two further        functional groups which are chosen from hydroxyl, primary and/or        secondary amino groups,    -   and    -   b) at least one compound with a molecular weight in the range        from 56 to 600 which contains two active hydrogen atoms per        molecule,    -   c) at least one compound which has two active hydrogen atoms and        at least one ionogenic and/or ionic group per molecule,    -   d) optionally at least one polymer with at least two active        hydrogen atoms per molecule,    -   e) at least one diisocyanate.

These polyurethanes contain at least one of the oligomers as componenta) in incorporated (copolymerized) form.

EP 938 889 A2 describes an aqueous cosmetic composition comprising atleast one water-soluble or water-dispersible polyurethane of

-   -   a) at least one polymer with two active hydrogen atoms per        molecule which is chosen from polytetrahydrofurans,        polysiloxanes and mixtures thereof,    -   b) at least one polyesterdiol,    -   c) at least one compound with a molecular weight in the range        from 56 to 300 which contains two active hydrogen atoms per        molecule,    -   d) at least one compound which has two active hydrogen atoms and        at least one anionogenic or anionic group per molecule,    -   e) at least one diisocyanate,    -   or the salts thereof, where the polyurethane does not contain a        unit originating from a primary or secondary amine which has an        ionogenic or ionic group.

The polyurethanes described in EP 938 889 A2 are essentiallyuncrosslinked.

In contrast thereto, the polyurethanes according to the invention arecrosslinked.

None of the mentioned publications describes crosslinked polyurethanesbased on polytetrahydrofurans as in claim 1.

The present invention provides a crosslinked polyurethane comprising

-   -   A) at least one poolytetrahydrofuran of the formula    -   B) at least one compound which contains more than 2 active        hydrogen atoms per molecule    -   C) at least one compound which contains at least 2 active        hydrogen atoms per molecule and at least one ionogenic and/or        ionic group per molecule, where the groups may be anionogenic,        anionic, cationogenic or cationic    -   D) at least one diisocyanate    -   or the salts thereof.

Component A) is a polytetrahydrofuran of the formula

These polytetrahydrofurans usually have a number-average molecularweight in the range from 200 to 3000, preferably 250 to 2000, inparticular 600 to 1500.

Suitable polytetrahydrofurans can be prepared by cationic polymerizationof tetrahydrofuran in the presence of acidic catalysts, such as, forexample, sulfuric acid or fluorosulfuric acid. Such preparationprocesses are known to the person skilled in the art.

Component B) is a compound which contains more than 2 active hydrogenatoms per molecule.

Compounds suitable as component B) are those with more than 2 OH and/orNH groups. Compounds with 3 to 20, in particular 3 to 10, especially 3to 5, OH and/or NH groups are particularly suitable.

As component B), preference is given to using triols and higher polyolshaving 3 to 100, preferably 3 to 70, carbon atoms. Examples of preferredtriols are glycerol and trimethylolpropane. Preferred triols B) are alsothe triesters of hydroxycarboxylic acids with trivalent alcohols. Thecompounds are preferably triglycerides of hydroxycarboxylic acids, suchas, for example, lactic acid, hydroxystearic acid and ricinoleic acid.Also suitable are naturally occurring mixtures which containhydroxycarboxylic acid triglycerides, in particular castor oil.Preferred higher polyols B) are, for example, erythritol,pentaerythritol and sorbitol.

Preferred triamines B) are, for example, diethylenetriamine,N,N′-diethyldiethylenetriamine etc. Preferred higher polyamines are, forexample triethylenetetramine etc. and α,ω-diaminopolyethers, which canbe prepared by amination of polyalkylene oxides with ammonia.

The compounds specified as component B) can be used individually or inmixtures.

As component B), it is also possible to use polysiloxanes with more than2 active hydrogen atoms.

The polysiloxanes B) are, for example compounds of the formula II

in which

-   -   the order of the siloxane units is arbitrary,    -   s is a value from 5 to 200, preferably 10 to 100,    -   Z is a radical of the formula (Z-I) ═—(CH₂)_(u−)NH₂, in which u        is an integer from 1 to 10, preferably 2 to 6,    -   and/or    -   Z is a radical of the formula (Z-II)        ═—(CH₂)_(x)—NH—(CH₂)_(y)—NH₂, in which x and y, independently of        one another, are 0 to 10, preferably 1 to 6, while the sum of x        and y is 1 to 10, preferably 2 to 6,    -   t is a value from 3 to 20, preferably of 3 to 10, if Z=Z-I    -   t is a value from 2 to 20, preferably of 2 to 10, is Z=Z-II

These include, for example, the MAN and MAR products from Huls, and theFinish products from Wacker, e.g. Finish WT 1270.

Particularly suitable polyalkylene oxide-containing silicone derivativesare those which contain the following structural elements:

-   -   where x and y are integers such that the molecular weight of the        polysiloxane is between 300 and 30 000,    -   and where the radicals R¹ may be identical or different and        originating either from the group of aliphatic hydrocarbons        having 1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons        having 3 to 20 carbon atoms, or are aromatic in nature    -   and where the radicals R², R³, R⁵ may be identical or different        and originate either from the group of aliphatic hydrocarbons        having 1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons        having 3 to 20 carbon atoms, or are aromatic in nature or are        equal to R⁶, where:    -   with the proviso that at least one of the radicals R², R³ or R⁵        is a polyalkylene oxide-containing radical in accordance with        the above definition for R⁶ and n is an integer from 1 to 6, in        particular n=3,    -   a, b may be integers between 0 and 50 with the proviso that the        sum of a and b is greater than 0, where

Preferably, the groups R¹ are chosen from the following group: ethyl,ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl,dodecyl and octadecyl, cycloaliphatic radicals, specifically cyclohexyl,aromatic groups, specifically phenyl or naphthyl, mixedaromatic-aliphatic radicals, such as benzyl or phenylethyl, and tolyland xylyl.

Particular preference is given to methyl, ethyl and phenyl.

Preferably, the groups R², R³ and R⁵ are chosen from the followinggroup: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl,octyl, decyl, dodecyl and octadecyl, cycloaliphatic radicals,specifically cyclohexyl, aromatic groups, specifically phenyl ornaphthyl, mixed aromatic-aliphatic radicals, such as benzyl orphenylethyl, and tolyl and xylyl and R⁶.

Preferred radicals R² and R⁶ are those in which the sum of a+b isbetween 5 and 30.

In a particularly preferred embodiment of the present invention, thepolyalkylene oxide-containing silicone derivative B) used is a compoundof the following formula:

where

-   -   R¹═—CH₃    -   R⁴═—H; —COCH₃, alkyl with C₁-C₄, —OH    -   n=1 to 6, in particular 2 to 4, preferably 3,    -   where y is chosen so that at least 3 OH groups are present in        the molecule, i.e. when    -   x and y are integers such that the molecular weight of the        polysiloxane block is between 1000 and 10 000,    -   a, b may be integers between 0 and 50, with the proviso that the        sum of a and b is greater than 0.

As component B), it is also possible to use silicone-containingpolyamino compounds.

These are preferably a diaminopolyether siloxane of the formula IV whichis chosen from

-   -   polysiloxanes with repeat units of the formula IV.I        in which    -   a is an integer from 0 to 100,    -   b is an integer from 2 to 8,    -   R¹³ and R¹⁴, independently of one another, are C₁- to        C₈-alkylene,    -   the order of the alkylene oxide units is arbitrary and v and w,        independently of one another, are an integer from 0 to 200,        where the sum of v and w is >0,    -   polysiloxanes of the formula IV.2        in which    -   R¹⁵ is a C₁- to C₈-alkylene radical,    -   R¹⁶ and R¹⁷, independently of one another, are hydrogen, C₁- to        C₈-alkyl or C₅- to C₈-cycloalkyl, the order of the siloxane        units is arbitrary, c, d and e, independently of one another are        0 to 100, where the sum of c, d and e is at least 3, and where d        and e are chosen so that at least 3 active hydrogen molecules        are present,    -   f is an integer from 2 to 8,    -   Z¹ is a radical of the formula V        —R¹⁸—(CH₂CH₂O)_(g)(CH2CH(CH₃)O)_(h)—H   (V)        in which    -   the order of the alkylene oxide units is arbitrary and g and h,        independently of one another, are an integer from 0 to 200,        where the sum of g and h is >0,    -   R¹⁸ is a C₁- to C₈-alkylene radical        and mixtures thereof.

Polysiloxanes of the formula IV.2 with more than 2 active hydrogen atomsare those in which d is ≧3 when R¹⁶ and R¹⁷≠H; or d+e is ≧3 when R¹⁶,R¹⁷═H.

Preferably, in the formula IV.1, R¹³ and R¹⁴, independently of oneanother, are a C₂- to C₄-alkylene radical. In particular, R¹³ and R¹⁴,independently of one another, are a C₂- to C₃-alkylene radical.

Preferably, the molecular weight of the compound of the formula IV.1 isin a range from about 300 to 100 000.

Preferably, in the formula IV.1, a is an integer from 1 to 20, such as,for example 2 to 10.

The total number of alkylene oxide units in the compound of the formulaIV.1, i.e. the sum of v and w, is preferably in a range from about 3 to200, preferably 5 to 180.

The end-groups of the polysiloxanes with repeat units of the formulaIV.1 are preferably chosen from (CH₃)₃SiO, H, C₁- to C₈-alkyl andmixtures thereof.

Suitable alkoxylated siloxaneamines of the formula IV.1 are described,for example, in WO-A-97/32917, to the entire contents of which referenceis hereby made. Commercially available compounds are, for example, theSilsoft® products from Witco, e.g. Silsoft® A-843.

Preferably, in the formula IV.2, the radical R¹⁵ is a C₂- to C₄-alkyleneradical.

Preferably, in the formula IV.2, R¹⁶ and R¹⁷, independently of oneanother, are hydrogen or C₁- to C₄-alkyl.

Preferably, the sum of c, d and e is chosen so that the molecular weightof the compound of the formula IV.2 is in a range from about 300 to 100000, preferably 500 to 50 000.

The total amount of the alkylene oxide units of the radical of theformula V, i.e. the sum of g and h, is preferably in a range from about3 to 200, preferably 5 to 80.

Preferably, in the formula V, the radical R¹⁸ is C₂- to C₄-alkyl.

Preferably, in the formula V, the radical R¹⁹ is hydrogen or C₁- toC₄-alkyl.

A suitable compound of the formula IV.2 is, for example, Silsoft® A-858from Witco.

Component C) is a compound which has at least 2 active hydrogen atomsand at least one ionogenic and/or ionic group per molecule, where thegroups may be anionogenic, anionic, cationogenic and/or cationic.

Preferred compounds C) with two active hydrogen atoms and at least oneanionogenic and/or anionic group per molecule are, for example,compounds with carboxylate and/or sulfonate groups. As component C),2,2-hydroxymethylalkylcarboxylic acids, such as dimethylolpropanoicacid, and mixtures which contain 2,2-hydroxymethylalkylcarboxylic acids,such as dimethylolpropanoic acid, are particularly preferred.

Suitable diamines and/or diols C) with anionogenic or anionic groups arecompounds of the formula

in which R is in each case a C₂-C₁₈-alkylene group and Me is Na or K.

As component C), it is also possible to use compounds of the formulaH₂N (CH₂)_(w)—NH—(CH₂) _(x)—COO⁻M⁺H₂N (CH₂)_(w)—NH—(CH₂) x—SO₃ ⁻M⁺in which w and x, independently of one another, are an integer from 1 to8, in particular 1 to 6, and M is Li, Na or K, and compounds of theformulaH₂N(CH₂CH₂O)_(y)(CH₂CH(CH₃)O)_(z)(CH₂)_(w)—NH—(CH₂)_(x)—SO₃ ⁻M⁺in which w and x have the meanings given above, y and z, independentlyof one another, are an integer from 0 to 50, where at least one of thetwo variables y or z is >0. The order of the alkylene oxide units hereis arbitrary. The last-mentioned compounds preferably have anumber-average molecular weight in the range from about 400 to 3000. Asuitable compound of this type is, for example, Poly ESP 520 fromRaschig.

The polyurethanes can also contain, in each incorporated form, compoundsC) which have two active hydrogen atoms and at least one cationogenicand/or cationic group, preferably at least one nitrogen-containinggroup, per molecule. The nitrogen-containing group is preferably atertiary amino group or a quaternary ammonium group. Preference isgiven, for example, to compounds of the formulae

in which

-   -   R⁷ and R⁸, which may be identical or different, are        C₂-C₈-alkylene,    -   R⁹, R¹² and R¹³, which may be identical or different, are        C₁-C₆-alkyl, phenyl or phenyl-C₁-C₄-alkyl,        -   R¹⁰ and R¹¹, which may be identical or different, are H or            C₁-C₆-alkyl,        -   _(o) is 1, 2 or 3,        -   X⁷³ is chloride, bromide, iodide, C₁-C₆-alkyl sulfate or SO₄            ²⁻/₂.

Particular preference is given to using N—(C₁- toC₆-alkyl)diethanolamines, such as methyldiethanolamine, andN-alkyldialkylene triamines, such as N-methyldipropylene triamine. Theseare preferably used in combination with dimethylolpropanoic acid ascomponent C).

Also suitable as component C) are mixtures which comprise two or more ofthe abovementioned compounds with anionic and/or anionogenic groups, twoor more of the abovementioned compounds with cationic and/orcationogenic groups or mixtures which comprise at least one of theabovementioned compounds with anionic or anionogenic groups and at leastone of the abovementioned compounds with cationic or cationogenicgroups. Preference is given, for example, to using mixtures whichcomprise dimethylolpropanoic acid and N-methyldiethanolamine. Accordingto a preferred embodiment, the polyurethanes comprise predominantly orexclusively anionogenic and/or anionic groups as ionogenic and/or ionicgroups. According to a further preferred embodiment, the polyurethanescomprise predominantly or exclusively cationogenic and/or cationicgroups as ionogenic and/or ionic groups. Preferably, the polyurethanesthus comprise, in incorporated form, a component C) which comprisespredominantly, preferably in an amount of at least 80% by weight, inparticular in an amount of at least 90% by weight, based on the totalamount of component C), either anionogenic (anionic) compounds orcationogenic (cationic) compounds.

The diisocyanates D) are preferably chosen from aliphatic,cycloaliphatic and/or aromatic diisocyanates, such as tetramethylenediisocyanate, hexamethylene diisocyanate, methylenediphenyldiisocyanate, 2,4- and 2,6-tolylene diisocyanate and isomeric mixturesthereof, o-, m- and p-xylylene diisocyanate, 1,5-naphthylenediisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethanediisocyanate and mixtures thereof, in particular isophoronediisocyanate, hexamethylene diisocyanate and/or dicyclohexylmethanediisocyanate. Particular preference is given to using hexamethylenediisocyanate. If desired, up to 3 mol % of said compounds can bereplaced by triisocyanates.

Component E) is a compound different from B) and C) which contains atleast 2 active hydrogen atoms and has a molecular weight of from 60 to5000.

As component E), preference is given to using diols whose molecularweight is in a range from about 62 to 500 g/mol. These include, forexample, diols having 2 to 18 carbon atoms, preferably 2 to 10 carbonatoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol,1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, di-, tri-,tetra-, penta- and hexaethylene glycol, neopentyl glycol,cyclohexanedimethylol and mixtures thereof.

Preferred amino alcohols E) are, for example, 2-aminoethanol,2-(N-methylamino)ethanol, 3-aminopropanol, 4-aminobutanol,1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol,4-methyl-4-aminopentan-2-ol etc.

Preferred polyamines E) are, for example, diamines, such asethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentaneand 1,6-diaminohexane.

The compounds known as component E) can be used individually or inmixtures. Particular preference is given to using 1,2-ethanediol,1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol,cyclohexanedimethylol and mixtures thereof.

Component E) is preferably a polymer with a number-average molecularweight in the range from about 300 to 5000, preferably about 400 to4000, in particular 500 to 3000. Polymers E) which can be used are, forexample, polyesterdiols, polyetherols, polysiloxanes and mixturesthereof. Polyetherols are preferably polyalkylene glycols, e.g.polyethylene glycols, polypropylene glycols etc., copolymers of ethyleneoxide and propylene oxide or block copolymers of ethylene oxide,propylene oxide and butylene oxide which contain the copolymerizedalkylene oxide units in random distribution or in the form of blocks.Also suitable are α,ω-diaminopolyethers which can be prepared byamination of polyalkylene oxides with ammonia. Preference is given tousing polyesterdiols and mixtures which contain these as component E).

Preferred polyesterdiols have a number-average molecular weight in therange from about 400 to 5000, preferably 500 to 3000, in particular 600to 2000.

Suitable polyesterdiols are all those which are customarily used for thepreparation of polyurethanes, in particular those based on aromaticdicarboxylic acids, such as terephthalic acid, isophthalic acid,phthalic acid, Na or K sulfoisophthalic acid etc., aliphaticdicarboxylic acids, such as adipic acid or succinic acid etc., andcycloaliphatic dicarboxylic acids, such as 1,2-, 1,3- or1,4-cyclohexanedicarboxylic acid. Suitable diols are, in particular,aliphatic diols, such as ethylene glycol, propylene glycol,1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethyleneglycols, polypropylene glycols, 1,4-dimethylolcyclohexane.

Preference is given to polyesterdiols based on aromatic and aliphaticdicarboxylic acids and aliphatic diols, in particular those in which thearomatic dicarboxylic acid constitutes 10 to 95 mol %, in particular 40to 90 mol %, of the total dicarboxylic acid fraction (remainderaliphatic dicarboxylic acids).

Particularly preferred polyesterdiols are the reaction products ofphthalic acid/diethylene glycol, isophthalic acid/1,4-butanediol,isophthalic acid/adipic acid/1,6-hexanediol, 5-NaSO₃-isophthalicacid/phthalic acid/adipic acid/1,6-hexanediol, adipic acid/ethyleneglycol, isophthalic acid/adipic acid/neopentyl glycol, isophthalicacid/adipic acid/neopentyl glycol/diethyleneglycol/dimethylolcyclohexane and 5-NaSO₃-isophthalic acid/isophthalicacid/adipic acid/neopentyl glycol/diethyleneglycol/dimethylolcyclohexane, isophthalic acid/adipic acid, neopentylglycol/dimethylolcyclohexane.

Also preferred as component E) are polyesterdiols based on linear orbranched C₈- to C₃₀-di- or polycarboxylic acids and C₈- toC₃₀-hydroxycarboxylic acids. Preferred carboxylic acids andhydroxycarboxylic acids are, for example, azelaic acid, dodecanedioicacid, suberic acid, pimelic acid, sebacic acid, tetradecanedioic acid,citric acid, ricinoleic acid, hydroxystearic acid and mixtures thereof.The diol component used for the preparation of these polyesterdiols ispreferably 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 1,4-dimethylolcyclohexane, diethylene glycol and mixturesthereof.

As component E), it is also possible to use polysiloxanes of thefollowing formula

in which

-   -   R⁴ and R⁵, independently of one another are C₁- to C₄-alkyl,        benzyl or phenyl,    -   E¹ and E², independently of one another are OH or NHR⁶, where R⁶        is hydrogen, C₁- to C₆-alkyl or C₅- to C₈-cycloalkyl,    -   i and l, independently of one another, are 2 to 8,    -   k is 3 to 50,    -   and mixtures thereof.

Suitable alkyl radicals are, for example, methyl, ethyl, n-propyl,isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl etc. Suitable cycloalkylradicals are, for example, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl etc.

Preferably, R⁴ and R⁵ are both methyl.

These polysiloxanes E) preferably have a number-average molecular weightin the range from about 300 to 10 000, preferably 400 to 5 000.

Suitable compounds E) are also the polydimethylsiloxanes described inEP-A-227 816, to which reference is hereby made.

Preferably, only one of components B) or E) comprises a polysiloxane.

Preference is given to crosslinked polyurethanes comprising

-   -   15 to 50% by weight, in particular 20 to 35% by weight of A)    -   0.1 to 5% by weight, in particular 0.2 to 2% by weight of B)    -   8 to 20% by weight, in particular 10 to 15% by weight of C)    -   25 to 60% by weight, in particular 30 to 50% by weight of D)    -   0 to 15% by weight, in particular 0 to 10% by weight of E)

Very particular preference is given to crosslinked polyurethanescomprising

-   -   20 to 25% by weight of A)    -   0,5 to 1.5% by weight of B)    -   10 to 15% by weight of C)    -   40 to 50% by weight of D)    -   0 to 2% by weight of E)

Particular preference is given to crosslinked polyurethanes comprising

-   -   A) polytetrahydrofuran, in particular with a molecular weight of        from 200 to 3000, preferably 250 to 2000, particularly        preferably from 600 to 1500    -   B) trimethylolpropane (TMP)    -   C) dimethylolpropanoic acid (DPMA)    -   D) at least one diisocyanate, preferably hexamethylene        diisocyanate and/or isophorone diisocyanate    -   E) optionally neopentyl glycol.

The polyurethanes used in the compositions according to the inventionare prepared by reacting the compounds of components A), B), C), D) andoptionally E). The temperature is in a range from about 60 to 140° C.,preferably about 70 to 100° C. The reaction can be carried out withoutsolvents or in a suitable inert solvent or solvent mixture. Suitablesolvents are aprotic-polar solvents, e.g. tetrahydrofuran, ethylacetate, N-methylpyrrolidone, dimethylformamide and preferably ketones,such as acetone and methyl ethyl ketone. The reaction is preferablycarried out under an inert gas atmosphere, such as, for example, undernitrogen. The components are used in amounts such that the ratio of NCOequivalent of the compounds of component E) to equivalent of activehydrogen atom of components A), B), C) and D) is in a range from about0.8:1 to 1.25:1, preferably 0.85:1 to 1.2:1, in particular 1.05:1 to1.15:1. If the resulting polyurethanes still have free isocyanategroups, then these are finally deactivated by adding amines, preferablyamino alcohols. Suitable amino alcohols are those described previouslyas component C), preferably 2-amino-2-methyl-1-propanol.

The acid-containing polyurethanes can be converted into a water-solubleor water-dispersible form by partial or complete neutralization with abase.

The resulting salts of the polyurethanes generally have a bettersolubility in water or dispersibility in water than the unneutralizedpolyurethanes. The bases used for the neutralization of thepolyurethanes may be alkali metal bases, such as sodium hydroxidesolution, potassium hydroxide solution, soda, sodium hydrogen carbonate,potassium carbonate or potassium hydrogen carbonate and alkaline earthmetal bases, such as calcium hydroxide, calcium oxide, magnesiumhydroxide or magnesium carbonate, and ammonia and amines. Suitableamines are, for example, C₁-C₆-alkylamines, preferably n-propylamine andn-butylamine, dialkylamines, preferably diethylpropylamine anddipropylmethylamine, trialkylamines, preferably triethylamine andtriisopropylamine, C₁-C₆-alkyldiethanolamines, preferably methyl- orethyldiethanolamine and di-C₁-C₆-alkylethanolamines. Particularly foruse in hair-treatment compositions, 2-amino-2-methyl-1-propanol,diethylaminopropylamine and triisopropanolamine have proven useful forthe neutralization of the acid-containing polyurethanes. Theneutralization of the acid-containing polyurethanes can also beundertaken using mixtures of two or more bases, e.g. mixtures of sodiumhydroxide solution and triisopropanolamine. Depending on the intendeduse, the neutralization may be partial, e.g. to 20 to 40%, or complete,i.e. to 100%.

If a water-miscible organic solvent is used in the preparation of thepolyurethanes, then this can be subsequently removed by customarymethods known to the person skilled in the art, e.g. by distillation atreduced pressure. Prior to the removal of the solvent, water mayadditionally be added to the polyurethane. Replacing the solvent withwater gives a solution or dispersion of the polymer from which, ifdesired, the polymer can be isolated in the usual manner, e.g. by spraydrying.

The polyurethanes according to the invention have K values (measured inaccordance with E. Fikentscher, Cellulose-Chemie 13 (1932), pp. 58-64,on a 1% strength solution in N-methylpyrrolidone) in a range from 15 to90, preferably 20 to 60. Their glass transition temperature is generallyat least 0° C., preferably at least 20° C., especially preferably atleast 25° C. and specifically at least 30° C.

The polyurethanes according to the invention are particularly suitableas coatings for keratin-containing surfaces (hair, skin and nails). Ifthe polyurethanes according to the invention are dispersible in water,they can be applied in the form of aqueous microdispersions withparticle diameters of usually 1 to 150 nm, preferably 5 to 100 nm. Thesolids contents of the preparations are usually in a range from about0.5 to 20% by weight, preferably 1 to 12% by weight. Thesemicrodispersions do not generally require any emulsifiers or surfactantsfor their stabilization.

Preferably, the polyurethanes according to the invention can be in theform of a hair-treatment composition, in particular in the form of ahair spray. For use as hair-setting compositions, preference is givenhere to compositions which comprise polyurethanes whose glass transitiontemperature T_(g) is ≧20° C., preferably ≧30° C. The K value of thesepolymers is preferably in a range from 23 to 90, in particular 25 to 60.

The cosmetic compositions generally comprise the polyurethanes in anamount in the range from 0.2 to 20% by weight, based on the total weightof the composition.

The compositions are preferably hair-treatment compositions. These areusually in the form of an aqueous dispersion or in the form of analcoholic or aqueous-alcoholic solution. Examples of suitable alcoholsare ethanol, propanol, isopropanol etc.

The invention provides a hair cosmetic composition comprising

-   -   0.5 to 20% by weight of a crosslinked polyurethane as claimed in        any of the preceding claims    -   40 to 99% by weight, preferably 50 to 98% by weight, of at least        one solvent chosen from water, water-miscible solvents and        mixtures thereof    -   0 to 50% by weight of a propellant.

In addition, the hair-treatment compositions generally comprisecustomary cosmetic auxiliaries, for example softeners, such as glyceroland glycol; emollients; perfumes; UV absorbers; dyes; thickeners;antistats; agents for improving combability; preservatives; and foamstabilizers.

If the polyurethanes according to the invention are formulated as hairspray, they comprise an adequate amount of a propellant, for example alow-boiling hydrocarbon or ether, such as propane, butane, isobutane ordimethyl ether. Propellants which can be used are also compressed gases,such as nitrogen, air or carbon dioxide. The amount of propellant heremay be kept low in order not to unnecessarily increase the VOC content.It is then generally not more than 55% by weight, based on the totalweight of the composition. If desired, however, higher VOC contents of85% by weight and above are also possible.

The polyurethanes described above can also be used in combination withother hair polymers in the compositions. Such polymers are, inparticular:

-   -   nonionic, water-soluble or water-dispersible polymers or        oligomers, such as polyvinylcaprolactam, e.g.. Luviskol Plus        (BASF), or polyvinylpyrrolidone and copolymers thereof, in        particular with vinyl esters, such as vinyl acetate, e.g.        Luviskol VA 37 (BASF); polyamides, e.g. based on itaconic acid        and aliphatic diamines;    -   amphoteric or zwitterionic polymers, such as the        octylacrylamide/methyl methacrylate/tert-butylaminoethyl        methacrylate/2-hydroxypropyl methacrylate copolymers obtainable        under the names Amphomer® (Delft National), and zwitterionic        polymers, as are disclosed, for example, in German patent        applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37        08 451. Acrylamidopropyltrimethylammonium chloride/acrylic acid        or    -   methacrylic acid copolymers and alkali metal and ammonium salts        thereof are preferred zwitterionic polymers. Further suitable        zwitterionic polymers are methacroylethylbetaine/methacrylate        copolymers, which are commercially available under the name        Amersette® (AMERCHOL);    -   anionic polymers, such as vinyl acetate/crotonic acid        copolymers, as are available commercially, for example under the        names Resyn® (NATIONAL STARCH), Luviset® (BASF) and Gafset®        (GAF), vinylpyrrolidone/vinyl acrylate copolymers, obtainable,        for example, under the trade name Luviflex® (BASF). A preferred        polymer is the vinylpyrrolidone/acrylate terpolymer obtainable        under the name Luviflex® VBM-35 (BASF), acrylic acid/ethyl        acrylate/N-tert-butylacrylamide terpolymers, which are sold, for        example, under the name Ultrahold® strong (BASF), and Luvimer®        (BASF, terpolymer of t-butyl acrylate, ethyl acrylate and        methacrylic acid), or    -   cationic (quaternized) polymers, e.g. cationic polyacrylate        copolymers based on N-vinyllactams and derivatives thereof        (N-vinylpyrrolidone, N-vinylcaprolactam etc.), and customary        cationic hair-conditioning polymers, e.g. Luviquat® (copolymer        of vinylpyrrolidone and vinylimidazolium methochloride),        Luviquat® Hold (copolymer of quaternized N-vinylimidazole,        N-vinylpyrrolidone and N-vinylcaprolactam), Merquat® (polymer        based on dimethyldiallylammonium chloride), Gafquat® (quaternary        polymers which arise by reacting polyvinylpyrrolidone with        quaternary ammonium compounds), polymer JR        (hydroxyethylcellulose with cationic groups), polyquaternium        products (CTFA names) etc.;    -   nonionic, siloxane-containing, water-soluble or -dispersible        polymers, e.g. polyether siloxanes, such as Tegopren®        (Goldschmidt) or Belsil® (Wacker).

The inventive crosslinked polyurethanes based on at least onepolytetrahydrofuran are preferably used as the mixture with one otheramide-containing hair polymer. These include, for example, thepolyurethanes described in DE-A-42 25 045, the above-describedvinylpyrrolidone/acrylate terpolymers and acrylic acid/ethylacrylate/N-tert-butylacrylamide terpolymers (e.g. Ultrahold® strong fromBASF Aktiengesellschaft), the above-described amide-containingamphoteric polymers (e.g. Amphomer®) and, in particular, copolymerswhich have a content of amide-containing monomers, such asN-vinyllactams, of at least 30% by weight (e.g. Luviskol® plus andLuviskol® VA37 from BASF Aktiengesellschaft). Particular preference isgiven to mixtures of the polyurethanes with these amide-containing hairpolymers.

The other hair polymers are preferably present in amounts up to 10% byweight, based on the total weight of the composition.

A preferred hair-treatment composition comprises:

-   -   a) 0.5 to 20% by weight of at least one crosslinked polyurethane        as claimed in claim 1,    -   b) 40 to 99% by weight, preferably 50 to 98% by weight, of a        solvent chosen from water and water-miscible solvents,        preferably C₂- to C₅-alcohols, in particular ethanol, and        mixtures thereof,    -   c) 0 to 50% by weight of a propellant, preferably dimethyl        ether,    -   d) 0 to 15% by weight of at least one water-soluble or        -dispersible hair polymer different from a),    -   e) 0 to 0.2% by weight of at least one water-insoluble silicone,    -   f) 0 to 2% by weight of at least one nonionic,        siloxane-containing, water-soluble or -dispersible polymer.

The composition according to the invention can comprise, as componentd), at least one other water-soluble or -dispersible hair polymer. Thecontent of this component is then generally about 0.1 to 15% by weight,preferably 0.1 to 10% by weight, based on the total amount of thecomposition. Preference may be given here to using crosslinkedpolyurethanes which do not contain any copolymerized siloxane groups.

The composition according to the invention can comprise, as componente), at least one water-insoluble silicone, in particular apolydimethylsiloxane, e.g. the Abil® product from Goldschmidt. Thecontent of this component is then generally about 0.001 to 0.2% byweight, preferably 0.01 to 0.1% by weight, based on the total weight ofthe composition.

The composition according to the invention can comprise, as componentf), at least one nonionic, siloxane-containing, water-soluble or-dispersible polymer, in particular chosen from the above-describedpolyether siloxanes. The content of this component is then generallyabout 0.001 to 2% by weight, based on the total weight of thecomposition.

The composition according to the invention can optionally additionallycomprise a defoamer, e.g. based on silicone. The amount of defoamer isgenerally up to about 0.001% by weight, based on the total amount of thecomposition.

A particularly preferred hair-treatment composition comprises:

-   -   a) 0.5 to 20% by weight of at least one crosslinked polyurethane        as claimed in claim 1,    -   b) 50 to 98% by weight of a solvent chosen from water, ethanol        and mixtures thereof,    -   c) 0 to 50% by weight of a propellant,    -   d) 0.1 to 10% by weight of at least one water-soluble or        -dispersible, amide-containing, silicone-free hair polymer,    -   e) 0 to 0.1% by weight of at least one water-insoluble silicone,    -   f) 0 to 1% by weight of at least one nonionic,        siloxane-containing, water-soluble or -dispersible polymer    -   and customary additives.

In a preferred embodiment, the amide-containing hair polymer d) is apolymer which contains one or more copolymerized amide-containingmonomers. Preferred amide-containing monomers are N-vinyllactams, whichare preferably chosen from N-vinylpyrrolidone, N-vinylcaprolactam,derivatives thereof, which may, for example, have one or more C₁- toC₄-alkyl substituents, and mixtures thereof. The hair polymers d)comprise these then preferably in an amount of at least 30% by weight incopolymerized form. Also suitable is a polymer mixture which has atleast one such copolymer. Particular preference is given to theLuviskol® products from BASF Aktiengesellschaft, such as Luviskol VA37and Luviskol plus.

According to a further preferred embodiment, the amide-containing hairpolymer d) is a silicone-free polyurethane, as are described, forexample, in DE-A-42 25 045, DE-A-42 41 118 and EP-A-619 111.

The compositions according to the invention have the advantage that, onthe one hand, they impart the desired setting to the hair and, on theother hand, the polymers can be readily washed out (are redispersible),and they additionally make the hair smooth and/or shine. Moreover,hair-treatment compositions with a VOC content of less than 85% byweight, preferably less than 60% by weight, and also purely aqueousformulations, can be prepared even if they are formulated as hair spray.

The above inventive crosslinked polyurethanes of a polytetrahydrofuranand/or polysiloxane are also suitable as auxiliaries in pharmacy, suchas, for example, as coatings and/or binders for solid medicament forms.They can also be used in creams and as tablet coatings and tabletbinders. Furthermore, they are suitable for use as coatings for thetextile, paper, printing, leather and adhesive industries.

EXAMPLES Example 8

In a reaction vessel equipped with stirrer, dropping funnel,thermometer, reflux condenser and equipment for working under nitrogen,500 g [0.5 mol] of polytetrahydrofuran (Mn=1000 g/mol), 26.8 (0.2 mol)of trimethylolpropane (TMP), 201 g (1.5 mol) [lacuna], 228 g (2.2 mol)of neopentyl glycol (NPG) and 268 g (2 mol) of dimethylolpropanoic acid(DMPA) were dissolved in 370 g of methyl ethyl ketone with heating to atemperature of 80° C. and with stirring. As soon as everything haddissolved, the reaction mixture was cooled to about 50° C. Then, withstirring, a mixture of 588 g (3.5 mol) of hexamethylene diisocyanate and333 g (1.5 mol) of isophorone diisocyanate were added dropwise, duringwhich the reaction temperature increased. Under reflux, the reactionmixture was then stirred until the NCO content of the mixture remainedvirtually constant. The mixture was then cooled to RT. The reactionproduct was terminated and 90% neutralized with 161.3 g (1.8 mol) of2-amino-2-methyl-1-propanol (AMP)/water at a temperature of about 40° C.The solvent was then distilled off under reduced pressure at 40° C.,giving an aqueous dispersion. Pulverulent polyurethanes can be obtainedby spray drying.

Examples 1 to 13 were prepared accordingly.

The table below gives the composition and the performance properties.

Examples 1 to 5 are comparative examples,

Examples 6 to 13 are in accordance with the invention. TABLE Flexibilitygrade P(ester- PEG P(THF) A-Si (with AMP-neutralized Sticki- diol) 10001000 2122 TMP HDI NPG DMPA MDEA IPDI prod.) ness 1 1.0 — — — — — 1.2 2.5— 5 3 1 2 1.0 — — — — 3 1.2 2.5 — 2 2 1 3 0.5 0.5 — — — 5 1.2 2.5 — — 12-3 4 — 0.5 0.5 — — 3 1.2 2.5 — 2 1 2-3 5 — — 0.5 — — 4 2.2 2.5 — 1 11-2 6 — 0.3 0.7 — 0.3 3 1.2 2.5 — 1.7 1 1-2 7 — — 0.5 — 0.3 4 1.8 2.5 —1 1 1 8 — — 0.5 — 0.2 3.5 2.2 2.0 — 1.5 1 1 9 — — 0.5 — 0.2 3.5 2.2 1.70.3 1.5 1 1 10 0.1 — 0.4 — 0.2 3.5 2.2 2.0 — 1.5 1 1 11 — 0.1 0.4 — 0.23.5 2.2 2.0 — 1.5 1 1 12 — — 0.45 0.05 0.2 3.5 2 2.2 — 1.5 1 1 13 — 0.50.5 — 0.2 3 1.2 2.5 — 2 1 1P(Ester-diol): Polyesterdiol of isophthalic acid/adipicacid/hexanediol(1,6) MW ≈ 1000 g/molPEG 1000: Polyethylene glycol, MW ≈ 1000 g/molP(THF)1000: Polytetrahydrofuran, MW ≈ 1000 g/molA-Si2122: P(Dimethylsiloxanediamine), Mn ≈ 900 (Tegomer, Goldschmidt)NPG: Neopentyl glycolDMPA: Dimethylolpropanoic acidHDI: HexamethyldiisocyanateIPDI: Isophorone diisocyanateAMP: Amino-2-methylpropanolMDEA: N-MethyldiethanolamineTMP: TrimethylolpropanePerformance Investigations

The flexibility was determined by measuring the modulus of elasticity

Flexibility grade=modulus of elasticity (N/mm²): 1: very flexiblemodulus of elasticity ≦ 200 N/mm² 2: flexible modulus of elasticity =200 to 800 N/mm² 3: moderately flexible modulus of elasticity = 800 toabout 1400 N/mm² (can still be measured) 4: brittle (films with layerthickness of about 100 to 150 μm) cannot be punched out; cannot bemeasured

The stickiness was determined as follows.

A film (about 30 μm film layer thickness) was applied to a glass plateand stored overnight at 40° C. and 75% relative atmospheric humidity.The stickiness of the film was determined by a panel of experts.

-   -   Grade 1=not sticky    -   Grade 2=slightly sticky    -   Grade 3=sticky        Formulations

In order to demonstrate the use as hair-treatment compositions, thefollowing hair-treatment compositions were prepared: (a) Aerosolhairspray (purely ethanolic) Polyurethane as in Example 7 3.00%2-Amino-2-methylpropanol 0.26% Ethanol abs. 61.74% Dimethyl ether 35.00%(b) Aerosol hairspray (aqueous-alcoholic) Polyurethane as in Example 73.00% 2-Amino-2-methylpropanol 0.26% Water dist. 10.00% Ethanol abs.51.74% Dimethyl ether 35.00% (c) Hand pump spray Polyurethane as inExample 7 6.00% 2-Amino-2-methylpropanol 0.52% Water dist. 93.48% (d)Hair-setting composition (purely aqueous) Polyurethane as in Example 74.00% 2-Amino-2-methylpropanol 0.37% Water dist. 95.63% (e) Hair-settingcomposition (aqueous-alcoholic) Polyurethane as in Example 7 4.00%2-Amino-2-methylpropanol 0.37% Water dist. 63.75% Ethanol abs. 31.88%

1. A crosslinked polyurethane comprising A) at least onepolytetrahydrofuran of the formula

B) at least one compound which contains more than 2 active hydrogenatoms per molecule C) at least one compound which contains at least 2active hydrogen atoms per molecule and at least one ionogenic and/orionic group per molecule, where the groups may be anionogenic, anionic,cationogenic or cationic D) at least one diisocyanate E) optionally acompound different from B) and C) which contains at least 2 activehydrogen atoms and has a molecular weight of from 60 to 5000 or a saltthereof.
 2. A crosslinked polyurethane as claimed in claim 1, where thepolytetrahydrofuran A) has a molecular weight of from 200 to 3000,preferably 250 to
 2000. 3. A crosslinked polyurethane as claimed inclaim 1, where triols and/or triamines are used as component B).
 4. Acrosslinked polyurethane as claimed in claim 1 further comprising 15 to50% by weight, in particular 20 to 35% by weight, of A) 0.1 to 5% byweight, in particular 0.2 to 2% by weight, of B) 8 to 20% by weight, inparticular 10 to 15% by weight, of C) 25 to 60% by weight, in particular30 to 50% by weight, of D) 0 to 15% by weight, in particular 0 to 10% byweight of E) with the proviso that the components add up to 100%.
 5. Acrosslinked polyurethane as claimed in claim 1 further comprising A)polytetrahydrofuran, in particular with a molecular weight of from 200to 3000, preferably 250 to 2000, particularly preferably from 600 to1500. B) trimethylolpropane (TMP) C) dimethylolpropanoic acid (DPMA) D)at least one diisocyanate, preferably hexamethylene diisocyanate and/orisophorone diisocyanate. E) optionally neopentyl glycol.
 6. A haircosmetic composition comprising 0.5 to 20% by weight of a crosslinkedpolyurethane as claimed in claim 1 40 to 99% by weight, preferably 50 to98% by weight, of at least one solvent chosen from water, water-misciblesolvents and mixtures thereof 0 to 50% by weight of a propellant.
 7. Amethod for producing cosmetic and/or pharmaceutical auxiliariescomprising adding a crosslinked polyurethane as claimed in claim 1 to acosmetic and/or pharmaceutical auxiliaries formulation.
 8. A method asclaimed in claim 7 wherein said cosmetic and/or pharmaceuticalauxiliaries are film formers.
 9. A method for producing a coating,covering and/or binder for solid medicament forms comprising adding acrosslinked polyurethane as claimed in claim 1 to a coating, coveringand/or binder for solid medicament forms.
 10. A method for producing acoating comprising adding a crosslinked polyurethane as claimed in claim1 to a coating formulation wherein said coating is utilized in thetextile, paper, printing, leather and adhesive industries.